CN102460299A

CN102460299A - Photosensitive modified polyimide resin composition and use thereof

Info

Publication number: CN102460299A
Application number: CN2010800295544A
Authority: CN
Inventors: 五岛敏之; M.S.温; 濑川繁昌; 许荣花
Original assignee: PI R&D Co Ltd
Current assignee: Hefei hanzhihe New Material Technology Co.,Ltd.
Priority date: 2009-04-30
Filing date: 2010-04-30
Publication date: 2012-05-16
Anticipated expiration: 2030-04-30
Also published as: KR20120023025A; EP2426557A1; US8859170B2; CN102460299B; KR101716288B1; WO2010126133A1; US20120097435A1; JP2010260902A; JP5515394B2; EP2426557A4

Abstract

Disclosed are: a photosensitive modified polyimide resin composition having excellent electrical properties and adhesion properties, also having excellent heat resistance, flexibility, bending properties, low warpage properties, chemical resistance and storage stability, and having photo-fabrication properties; a resin film formed from the composition; a printed circuit board or a flexible printed circuit board (FPC), each of which has the film as an insulating and protective film or an interlayer insulation film; and others. The photosensitive modified polyimide resin composition comprises a modified polyimide containing a flexible structure (e.g., a polycarbonate) in the main chain and having a specific structure, a photosensitizer, a heat-curing agent, and a solvent.

Description

Photonasty modified polyimide resin composition and use thereof

Technical field

The present invention relates to electrology characteristic, adaptation excellence; And the photonasty modified polyimide resin composition with light appearance property (

) of thermotolerance, flexibility, subduing property, low warpage properties, chemical proofing, excellent storage stability and by the resin molding that said composition forms has this film as the printed wiring board of insulating protective film or interlayer dielectric or flexible printing wiring board (FPC) etc.

Background technology

In recent years, as the insulating protective film of flexible printed circuit board etc., use polyimide resin, polyamide-imide resin, urethane resin, epoxy resin etc.When making this circuit board, for form the pattern circuit, form wiring plate surface and pattern circuit protective seam, form interlayer dielectric etc. and use photosensitive material.Photosensitive material roughly can be divided into liquid-type and membranaceous type.Under any one situation, all necessary thermotolerance of cured film, electrology characteristic excellence, in addition flexibility, flexible resistance, low warpage properties etc. also must be excellent.Polyimide is a large amount of the use because thermotolerance, electrology characteristic are excellent, but itself is upright and outspoken, has therefore proposed to improve through the whole bag of tricks.Wherein a kind of is the so-called mixed type that mixes the resinous principle with flexibility at polyimide or in as the polyamic acid of its precursor, and another kind is that softening compositions polysiloxane structure etc. is imported to the so-called modification type in the polyimide main chain.

As the photosensitive material of mixed type, the dry film photoresist that contains polyimide resin, (methyl) acrylic resin is disclosed in the patent documentation 1.But, mostly add a large amount of (methyl) acrylic acid series compounds in order to realize the giving of curable, low temperature plyability, because employed (methyl) acrylic acid series compound, thermotolerance reduces, and might damage the excellent specific property of polyimide.In addition, be necessary to consider the compatibility etc. between the resin, during the compatibility significance difference, the uneven increase in the face of sensitometric characteristic, the reliability of pattern precision, thickness etc. might reduce.

As the photosensitive material of modification type, disclose in the patent documentation 2 to comprise and derived forming of the silicone-modified polyimide that obtains by the diamido polysiloxane.The thermotolerance of silicone-modified polyimide, electrical insulating property excellence, and elasticity is low, so low warpage properties is excellent.But owing to be the polysiloxane composition, the adaptation on cured film surface is insufficient, the problem of dispersing of the annular siloxane that produces when having heat in addition.

On the other hand, in the patent documentation 3 of non-photosensitive material, disclose polycarbonate modified polyimide resin, disclose the composition that comprises ester modified polyimide resin in the patent documentation 4.The low warpage properties of these compositions is excellent, and the problem of the adaptation on the cured film surface of finding in the silicone-modified polyimide, the problem of generation annular siloxane improve.Infer through in these modified resin; Such as patent documentation 1 the record; Wait and mix photosensitive polymer combination through adding (methyl) acrylic resin; Photonasty be can give, the composition of main composition material, the trend of similar problem in mixed type formed for the resin of non-photosensitive but exist to produce problem uneven in the face of sensitometric characteristic etc.In addition, owing to there is the independent low trend of chemical proofing of each resin, described in patent documentation, must add epoxy resin, storage stability has the trend of reduction.

Therefore infer and be not mixed system but be the righttest the method that modified polyimide is given sensitometric characteristic.Disclose in the patent documentation 5 to comprise and have ether acid imide skeleton, polycarbonate skeleton and urethane bond, side chain has the composition that development property group, main chain end have the polyimide resin of photonasty group.Wherein, the photonasty group uses (methyl) acryloyl group, further forms the composition that comprises (methyl) acrylate compounds, Photoepolymerizationinitiater initiater, thermal polymerization.Yet, though improve, be necessary to add epoxy resin or isocyanate compound as hardening agent owing to so-called negative-type photosensitive makes the solvent resistance of cured film, therefore there is the problem of storage stability difference.In addition, must when synthesis of polyimides, there be the synthetic difficulty that is prone to gelation to importing (methyl) acryloyl groups such as end of polyimide chain.That is, must be noted that (methyl) acryloyl group can the heat when synthetic not react, the viscosity management also is not easy.On the contrary, influential if add polymerization inhibitor then to hinder curing reaction during sensitization to goods, not the problem that can simply solve therefore.

As resin combination, if consider storage stability, then supposition formation is that the positive light sensitivity of representative is easy with the phenolic novolac.Specifically, the method for importing hydroxyl or carboxyl is suitable in the main chain of modified polyimide.But like 3,4 records of patent documentation, modified polyimide is owing to through tetracarboxylic dianhydride and di-isocyanate reaction are synthesized, can not import hydroxyl or carboxyl.That is, hydroxyl or carboxyl because and isocyanate reaction, be consumed with modes such as cross-linking reactions.Owing to likewise make C-terminal ether acid imide oligomer, diol compound, (compound), diisocyanate cpd reaction, be difficult to protect required hydroxyl in the patent documentation 5 with (methyl) acryloyl group.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2003-167336 communique

Patent documentation 2: TOHKEMY 2002-174896 communique

Patent documentation 3: TOHKEMY 2002-145981 communique

Patent documentation 4: TOHKEMY 2008-297388 communique

Patent documentation 5: TOHKEMY 2009-69664 communique.

Summary of the invention

Problem of the present invention provides electrology characteristic, adaptation is excellent; And the photonasty modified polyimide resin composition with light appearance property of thermotolerance, flexibility, subduing property, low warpage properties, chemical proofing, excellent storage stability and by the resin molding that said composition forms has this film as the printed wiring board of insulating protective film or interlayer dielectric or flexible printing wiring board (FPC) etc.

The application inventor studies intensively; The result finds; The resin combination that contains modified polyimide, emulsion and thermal curing agents with ad hoc structure, electrology characteristic, adaptation are excellent, and thermotolerance, flexibility, subduing property, low warpage properties, chemical proofing, excellent storage stability; Performance light appearance property; Said modified polyimide with ad hoc structure has the soft structure that is formed by the repetitive that contains carbonate group, ester group or urethane groups, has free hydroxyl and/or carboxyl in the main chain simultaneously, thereby accomplishes the present invention.

That is, the present invention provides photonasty modified polyimide resin composition, and said composition contains modified polyimide, emulsion, thermal curing agents and the solvent shown in the formula (I),

[Chemical formula 1]

(in the formula; R representes independently that respectively carbon number is 1～18 alkylidene, and X representes carbonate group, ester group or urethane groups respectively independently, and Y representes independently that respectively carbon number is 1～18 alkylidene or arlydene; A representes to remove the divalent organic group that the amino of diamines forms; The quadrivalent organic radical group that the carboxyl of tetrabasic carboxylic acid forms is removed in Z and Z ' expression, and among A, Z and the Z ' any at least one has free hydroxyl and/or carboxyl, and m, p, q represent 1～20 integer independently of each other).

In addition, the present invention provides through heating with the composition film forming of the invention described above, with resulting film and removes the photosensitive resin film that above-mentioned solvent obtains.Further; The present invention provides the manufacturing approach of patterning polyimide resin film; This method has the step that the composition of the invention described above is coated on film forming on the substrate, and the step that above-mentioned solvent is removed in resulting film heating is carried out step of exposing to the above-mentioned composition of having removed solvent through mask; Be heated to the above step of solidification temperature of above-mentioned hardening agent after exposure back step of developing and the development.Further, the present invention provides the printed wiring board or the FPC of the polyimide resin film with patterning of making through the method for the invention described above.

According to the present invention; The modified polyimide resin thickener that obtain at room temperature to preserve, storage stability is good; Can make photosensitive resin film in addition; Formed filming is that electrology characteristic, adaptation are excellent, and thermotolerance, flexibility, subduing property, low warpage properties, the excellent resin molding of chemical proofing.

Embodiment

As stated, photosensitive polymer combination of the present invention comprises the photonasty modified polyimide with the structure shown in the above-mentioned general formula (I).Below the preparation method of this photonasty modified polyimide is described, also preferred photosensitive polyimide is described simultaneously.

The modified polyimide that contains in the resin combination of the present invention preferably through will with the end shown in the formula (II) be isocyanates oligomer as must composition the end shown in the formula (III) that obtains of reaction be the method for the oligomer of acid anhydrides as the raw material of polyimide reaction; That is, making the end shown in the formula (III) is that the oligomer of acid anhydrides further reacts the method for carrying out polyimideization with diamines and tetracarboxylic dianhydride and prepares.

[Chemical formula 2]

(in the formula, the definition of R, Y, X, m and n respectively with above-mentioned general formula (I) in their definition separately identical).

[chemical formula 3]

(in the formula, the definition of R, Y, X, Z, m, n and p respectively with above-mentioned general formula (I) in their definition separately identical).

End shown in the above-mentioned general formula (III) be acid anhydrides oligomer through with the di-isocyanate reaction shown in diol compound shown in the general formula (IV) and the general formula (V), with tetracarboxylic dianhydride reaction, can import in the acid imide main chain then,

[chemical formula 4]

(in the formula, the definition of R, Y and m respectively with above-mentioned general formula (I) in their definition separately identical).

[chemical formula 5]

(in the formula, the definition of Y is identical with Y in the above-mentioned general formula (I)).

Diol compound shown in the above-mentioned general formula (IV), preferred R is the diol compound of aliphatic hydrocarbon.Can use the diol compound that contains some aromatic ring, but high resiliencyization, warpage properties aspect are prone to have problems.In addition, if when the amount of linking group X in the diol compound increases then high elastic modulusization, thermotolerance has the trend of reduction.Here employed diol compound number-average molecular weight is preferably 500～10000, and more preferably 800～5000.If number-average molecular weight is difficult to obtain preferred flexibility less than 500, if surpassing 10000 viscosity, mean molecular weight raises and the operability variation in addition.Specifically, can enumerate PCDL, polyester-diol, polyurethane diol,, be preferably general formula (VI) as the PCDL that uses among the present invention

[chemical formula 6]

(in the formula, the definition of R and m respectively with above-mentioned general formula (I) in their definition separately identical);

Shown PCDL.In the general formula (VI), the carbon number of the alkylidene that R representes is preferably 2～8, and in addition, m is preferably 6～16.Preferred concrete example as this PCDL; Can enumerate ProductName デュラノー Le T6001 that the ケミカ Le ズ of Asahi Chemical Industry (strain) produces, T5651, T4691 etc., commercially available article such as the ProductName PLACCEL CD-210 that ダイセ Le chemistry (strain) is produced, CD-210PL, CD-210HL.In addition, as polyester-diol, be preferably general formula (VII)

[chemical formula 7]

(in the formula, the definition of R and m respectively with above-mentioned general formula (I) in their definition separately identical)

Shown polyester-diol, preferred R and m are identical with situation in the general formula (VI).As the preferred concrete example of this polyester-diol, can enumerate ProductName PLACCEL 210 that the chemistry of ダイセ Le for example (strain) produces, 210N, L212AL etc.In addition, also can use through making diisocyanate cpd and excessive diol compound react the polyurethane diol oligomer that synthesizes.As this polyurethane diol oligomer, be preferably general formula (VIII)

[chemical formula 8]

Shown polyurethane diol oligomer, preferred R and m are identical with situation in the general formula (VI).

These diol compounds separately or more than 2 kinds combination use.

In addition, the diisocyanate shown in the above-mentioned general formula (V) is so long as to have carbon number be 1～18 alkylidene or arlydene does not then limit especially as the diisocyanate that has 2 NCOs in Y, 1 molecule.Can enumerate for example aliphatics, alicyclic or aromatic diisocyanate, be preferably the carbon number of removing NCO and be 1～18 aliphatics, aliphatics, alicyclic or aromatic diisocyanate.When using aromatic diisocyanate, compare during with the use aliphatic diisocyanate, the thermotolerance of modified polyimide resin improves, and has the trend of high elastic modulusization.As concrete diisocyanate, can enumerate 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1; 6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, IPDI, 1; Two (isocyanates methyl) cyclohexanes, 1 of 3-, two (isocyanates methyl) cyclohexanes, 4 of 4-, 4 '-dicyclohexyl methyl hydride diisocyanate, 3,3 '-dimethyl-4; 4 '-dicyclohexyl methyl hydride diisocyanate, benzal-2,4-diisocyanate, benzal-2,5-diisocyanate, benzal-2; 6-diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 1,5-naphthalene diisocyanate, 2; 6-naphthalene diisocyanate, 2, two (4-Phenoxyphenyl) propane-4 of 2-, 4 '-diisocyanate etc.In addition, for example also can use ProductName デュラネート D101 that the ケミカ Le ズ of Asahi Chemical Industry (strain) produces, D201 etc. to have the terminal modified compound of isocyanates.In addition,, also can use the isocyanates more than 3 yuan, can enumerate 3 yuan of isocyanate compounds such as ProductName デュラネート TPA-100 that the ケ of Asahi Chemical Industry ミカ Le ズ (strain) for example produces with degree that can not gelation in order to improve solvent resistance.And, above-mentioned isocyanate compound, for fear of through the time change, can use isocyanate compound with blockizations such as alcohol, phenol, oximes.

The proportion optimization of the diisocyanate shown in carbonic ester glycol shown in the above-mentioned general formula (IV) and the above-mentioned general formula (V) is NCO number/hydroxy number=1.1～2.5.If NCO number/hydroxy number raises less than 1.1 viscosity, when the imidizate of subsequent step, become problem.In addition, if NCO number/hydroxy number only is to be prone to produce the reaction between the isocyanates greater than 2.5, nonsensical.

Reaction can be carried out in the presence of solvent-free or organic solvent.Temperature of reaction is preferably 40 ℃～180 ℃, and the reaction time can suitably be selected according to reaction conditions, scale etc., for example is about 30 minutes～2 hours.

Through making the end shown in the general formula (II) that so obtains is that the oligomer and the tetracarboxylic dianhydride of isocyanates reacts to synthesize the tetracarboxylic dianhydride's oligomer shown in the general formula (III).Do not limit wherein employed tetracarboxylic dianhydride is special, specifically, can enumerate pyromellitic acid anhydride, 3,3 ', 4; 4 '-biphenyl tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3; 3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, 2, two (3,4-dicarboxyl phenyl) the propane dianhydrides, 4 of 2-; 4 '-(4,4 '-isopropylidene, two phenoxy groups) two phthalandione dianhydrides, 2, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-, ethylenebis (trimellitate) dianhydride, TOPOT 2,2 aromatic tetracarboxylic acids such as (trimellitic acid monoesters acid anhydrides) base dianhydride, 1,2; 4,5-cyclohexane tetracarboxylic dianhydride, 3,3 ', 4; 4 '-dicyclohexyl tetracarboxylic dianhydride, dicyclo [2.2.2] suffering-7-alkene-2,3,5, alicyclic tetracarboxylic dianhydrides such as 6-tetracarboxylic dianhydride.These tetracarboxylic dianhydrides use more than 2 kinds alone or in combination.

End shown in the general formula (II) is that oligomer and the tetracarboxylic dianhydride's of isocyanates proportion optimization is acid anhydride/NCO=more than 1.1.If acid anhydride/NCO raises less than 1.1 viscosity, when the imidizate of subsequent step, become problem.Number-average molecular weight as concrete tetracarboxylic dianhydride's oligomer is preferably 500～10000, and more preferably 1000～9000.If number-average molecular weight has the trend of variation less than 500 warpage properties, reduce if surpass the reactivity of the acid anhydrides of 10000 ends, exist to be difficult to import to the trend in the polyimide main chain.

Temperature of reaction is preferably 80 ℃～200 ℃, and the reaction time can suitably be selected according to reaction conditions, scale etc., for example is about 30 minutes～3 hours.The tetracarboxylic dianhydride's oligomer that so obtains can use poor solvent such as methyl alcohol to separate, but since less economical, most preferably directly carry out the imidizate step.

Through said method, obtain the tetracarboxylic dianhydride's oligomer shown in the general formula (III).N in the general formula (III) is 1～20 integer, is preferably 1～4 integer, and p is 1～20 integer, is preferably 1～8 integer, and the amount ratio that preferably sets reacted constituent is to fall into these scopes.

The tetracarboxylic dianhydride of tetracarboxylic dianhydride's oligomer shown in the general formula that so obtains (III) and use as required and the diamines that at least a portion contains hydroxyl or carboxyl are dissolved in the organic solvent; Direct imidizate can prepare thus and has hydroxyl or/and the soft structurally-modified polyimide resin of carboxyl.The mixing ratio of whole tetracarboxylic dianhydrides and diamines, with respect to 1 mole of % of total amount of acid dianhydride, the total amount of preferred diamines is 0.95～1.05 mole of %.Synthetic method can be used known method, can use the chemical imidizate that utilizes acetic anhydride/triethylamine system, valerolactone/catalyzer such as pyridine system suitably.

To wherein qualification especially of employed diamine compound; But because characteristics such as flexibility, subduing property, low warpage properties are given through soft structure positions such as polycarbonate structures; With the aliphatics of thermotolerance, chemical proofing difference, alicyclic comparing, can preferably use aromatic diamine.As diamines, specifically, can enumerate 1,3-diamido-4-hydroxy benzenes, 1,3-diamido-5-hydroxy benzenes, 1 with hydroxyl or carboxyl; 4-diamido-2-hydroxy benzenes, 1,3-diamido-4,6-dihydroxy benzenes, 1,4-diamido-2,5-dihydroxy benzenes, 3; 3 '-diamido-4,4 '-dihydroxy-1,1 '-biphenyl, 4,4 '-diamido-3,3 '-dihydroxy-1; 1 '-biphenyl, 3,3 '-diamido-4,4 '-dihydroxy-diphenyl sulfone, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas, 2 of 2-; 5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4 '-diaminodiphenyl-methane-3,3 '-dicarboxylic acid etc.These diamines use more than 2 kinds alone or in combination.

In addition, in order to improve thermotolerance, chemical proofing and adjustment developing performance, can use the diamines that does not contain hydroxyl or carboxyl simultaneously.Specifically, can enumerate m-phenylene diamine, p-phenylenediamine (PPD), 2,4-diaminotoluene, 2,6-diamino-pyridine, 2; 6-diamido-4-picoline, 4,4 '-diamido-2,2 '-dimethyl-1,1 '-biphenyl, 4; 4 '-diamido-3,3 '-dimethyl-1,1 '-biphenyl, 3,4 '-diamino-diphenyl ether, 4; 4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 4; 4 '-diamino-diphenyl thioether, 1, two (3-amino-benzene oxygen) benzene, 1 of 3-, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (4-amino-benzene oxygen) benzene, 2 of 4-; Two (4-aminophenyl) propane of 2-, α, α-two (4-aminophenyl)-1,3-diisopropyl benzene, α, α-two (4-aminophenyl)-1; 4-diisopropyl benzene, [3-(4-amino benzoyl) oxygen base phenyl]-4-Aminobenzoate, [4-(4-amino benzoyl) oxygen base phenyl]-4-Aminobenzoate, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 4; 4 '-(9-fluorenylidene) diphenylamine, 5 (6)-amino-1-(4-aminophenyl)-1,3,3-trimethyl indane, 4; 4 '-diamido-2,2 '-two (trifluoromethyl)-1,1 '-biphenyl, 2; Two (4-aminophenyl) HFC-236fas, 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 2 of 2-, two (3-amino-4-aminomethyl phenyl) HFC-236fas of 2-etc.These diamines use more than 2 kinds alone or in combination.

In addition, in order to improve chemical proofing, can import reactive group in the end portion of modified polyimide.For example add many slightly tetracarboxylic dianhydrides' amount and synthesize so that the end of modified polyimide forms acid anhydrides, then adding with 3-ethinyl aniline, 4-ethinyl aniline is the amines of representative, can import acetyl group in polymer ends thus.In addition, add the amount of many slightly diamine compounds and synthesize to form the amine end, then adding with maleic anhydride, ethinyl anhydride phthalic acid, phenylacetylene base anhydride phthalic acid is the acid anhydrides of representative, can likewise import two keys, triple bond as reactive group thus.React through the heating more than 150 ℃ between these end groups, main polymer chain is crosslinked.

In addition, as the tetracarboxylic dianhydride who here uses as required, can use and above-mentioned general formula (III) synthetic in the identical tetracarboxylic dianhydride of tetracarboxylic dianhydride that uses, can be identical or different with the tetracarboxylic dianhydride that uses in general formula (III) synthetic.

In addition; In the modified polyimide composition of the present invention; The ratio of the weight of the weight of the modified polyimide of the weight of soft structure (repetitive that the number of repeat unit in the above-mentioned general formula (I) is represented with said n) during with preparation (wherein; When Y is aromatic series except the weight of Y) be preferably 0.3～0.7, more preferably 0.4～0.65.If can not satisfy low warpage properties less than 0.3, if surpass the trend that 0.7 thermotolerance, chemical proofing have reduction.

The number-average molecular weight of the polyimide resin that so obtains is preferably 6000～60000, and more preferably 7000～50000.If number-average molecular weight has the trend of reduction less than 6000 film rerum naturas such as fracture strength, if be difficult to obtain the suitable thickener of operability above 60000.

Through said method, obtain the modified polyimide shown in the above-mentioned general formula (I).In the general formula (I), q is preferably 1～10, and oligomer and the above-mentioned diamines and the tetracarboxylic dianhydride's reaction that preferably make general formula (III) are so that q falls into this scope.

As the synthetic that uses among the present invention, can use under 25 ℃ vapor pressure as below the 3mmHg, the solvent below the 1mmHg more preferably.Specifically, can enumerate gamma-butyrolacton, triglyme, tetraethylene glycol dimethyl ether, methyl benzoate, ethyl benzoate, ethyl carbitol acetic acid esters, acetate of butyl carbitol etc., they can use more than 2 kinds alone or in combination.In addition, the thinning agent as being used to prepare resin combination time adjustment viscosity can use carbonates solvents such as ketones solvent, ethylene carbonate, propylene carbonate such as cyclohexanone.

Photonasty modified polyimide resin composition of the present invention contains above-mentioned modified polyimide, emulsion, thermal curing agents and solvent.

The modified polyimide that uses among the present invention; Owing to can control alkali dissolution speed through the amount of hydroxyl or carboxyl; The negative-type photosensitive both of the positive light sensitivity of exposed portion dissolving and unexposed portion dissolving maybe, but that composition of the present invention preferably has is must height meticulous, can not produce the positive light sensitivity of problems such as swelling during high resolving power.

Under the situation of negative-type photosensitive; Emulsion is to be the optical free radical generation agent of representative with benzoin class, acylphosphine oxide class; Be the light acid propellant of representative or be the photoreaction initiator such as light alkali propellant of representative with

salt, and produce the monomer or the polymkeric substance of polymerizations, cross-linking reaction through these initiating agents with the nitrobenzyl carbamate.As employed monomer here, can enumerate for example (methyl) acrylic acid series compound such as glycol diacrylate.The content of this negative photosensitive agent in resin combination with respect to polyimide 100 weight portions, is generally about 10～100 weight portions, is preferably about 20～60 weight portions.

Under the situation of positive light sensitivity,, so long as usually can be, can preferably use adjacent naphthoquinones two triazo-compounds of the easiest acquisition as the then especially use of the emulsion of novolac resin class as emulsion with limiting.Usually the emulsion of using adjacent naphthoquinones two nitrine sulfonic acid chlorides and compound reaction to form with phenol property hydroxyl.As the compound of phenol property, can enumerate for example phenol, p-dihydroxy-benzene, resorcinol, catechol, 2,4 dihydroxyl benzophenone, 2,3,4-trihydroxybenzophenone, 2; 2 ', 4,4 '-tetrahydroxybenzophenone, 2,3,4; 4 '-tetrahydroxybenzophenone, 2,2 ', 3,4,4 '-pentahydroxybenzophenone, 2; 4-resacetophenone, 2,5-resacetophenone, 2,6-resacetophenone, 3,5-resacetophenone, 2,3; 4-trihydroxy-acetophenone, 2,4,6-trihydroxy-acetophenone, 2, two (4-hydroxy phenyl) propane of 2-, α, α; α '-trimethyl-α, α ', α '-three (p-hydroxybenzene) P-xylene, 2, two (4-hydroxy phenyl) HFC-236fas of 2-, two (4-hydroxy phenyl) methane, two (4-hydroxy phenyl) sulfone, 4,4 '-biphenyl glycol, 2; Two (2,3, the 4-trihydroxy phenyl) propane, 4 of 2-, 4 '-dihydroxy phenyl sulfone etc.Positive type light sensitive agent such as adjacent naphthoquinones two nitrine sulfonate compounds with these structures separately or more than 2 kinds combination use.The content of this positive type light sensitive agent in resin combination with respect to polyimide 100 weight portions, is generally about 5～30 weight portions, is preferably about 10～25 weight portions.

As the hardening agent that contains in the resin combination of the present invention; Can enumerate エピコート 828 epoxy compounds, 2 such as (productions of oiling シェ Le society); 2 '-(1, the 3-phenylene) two-2-

azoles quinoline

isoxazoline compounds such as (productions of three states pharmaceuticals industry society), BF-BXZ (little westernization society produce) wait bismaleimidess such as benzo

piperazine compound, BMI-1000 (big with change into society's production) etc.These hardening agent separately or more than 2 kinds combination use.In addition, the content of this hardening agent in resin combination with respect to polyimide 100 weight portions, is generally about 5～30 weight portions, is preferably about 10～25 weight portions.

Resin combination of the present invention can be that above-mentioned each composition is included in the fluid composition in the solvent, also can be the composition of solvent-laden drying type not.As solvent, can directly use the reaction dissolvent that uses in the preparation of modified polyimide, preferred solvent is as stated.

There is the problem of using the unresolved anti-flammability of resin in order to satisfy low warpage properties separately in modified polyimide resin composition of the present invention.Therefore, the purposes for essential anti-flammability with respect to modified polyimide resin 100 weight portions, preferably contains non-halogenated flame retardant 1～20 weight portion, more preferably 2～15 weight portions.As non-halogenated flame retardant; So long as can significantly not reduce the non-halogenated flame retardant of sensitometric characteristic; Then do not limit especially; As the fire retardant that can be dissolved in the organic solvent, can use phosphorus flame retardants such as phosphate based compound, phosphonitrile (Off ォス Off ァゼ Application) based compound, triphenyl, ring-type phenoxy phosphazene especially suitably.In addition, be inorganic combustion inhibitor as non-halogen, can enumerate the hydrate of aluminium of metal hydrate flame retardant etc., they can separately or make up more than 2 kinds and use.

In addition, in modified polyimide resin composition of the present invention, can add colorants such as phthalocyanine blue, phthalocyanine green, filling agents such as silicon dioxide with the degree that does not influence sensitometric characteristic as required.In addition, can also add photosensitizer, alkali dissolution promoter, driving fit auxiliary agent, foam-breaking agent, levelling agent etc.

So the modified polyimide resin composition of preparation can be coated with machine, roll coater, spin coater, serigraphy through rod and waits and be coated with.In addition, also can use the modified polyimide resin composition to make the photonasty protective seam.In addition, this moment, the imbedibility when improving thermocompression bonded can use plastifier such as (methyl) acrylic acid series compound.

In addition, can photonasty modified polyimide resin composition of the present invention be processed membranaceously, operate with the form of dry film.At this moment, preferably contain (A) alkali solubility polyimide resin, (B) emulsion, (C) plastifier.Through containing plastifier because the Tg of composition reduces, have be prone to press glue, the effects such as warpage reduction when processing dry film.

Plastifier in the photonasty modified polyimide resin composition that the present invention relates to so long as can invest the plastifier of the Tg of plasticity, reduction composition to resin combination, does not then limit especially.As this plastifier; Can enumerate ether compounds such as polyglycol, polypropylene glycol, crown ether; TEG dimethylacrylate, polyethylene glycol dimethacrylate etc. contain the compound of methacryl, and tetraethylene glycol diacrylate, polyethyleneglycol diacrylate etc. contains the compound of acryloyl group, phthalate esters such as dimethyl phthalate ester, diethyl phthalate ester; Trimellitic acid esters such as three (2-ethylhexyl) trimellitate; Fatty group dibasic acids such as dimethyl adipate, dibutyl adipate, phosphates such as trimethyl phosphate, three (butoxyethyl group) phosphate, (C ₆H ₅O) ₂P (O) OC ₆H ₄C (CH ₃) ₂C ₆H ₄OP (O) (OC ₆H ₅) ₂Shown aromatic condensation phosphate, the glycol-modified diacrylate of isocyanuric acid, the glycol-modified diacrylate of isocyanuric acid etc.Wherein, consider, more preferably contain the glycol-modified diacrylate of compound, isocyanuric acid and the glycol-modified diacrylate of isocyanuric acid of methacryl from the warpage aspect of processing behind the dry film.

In the photonasty modified polyimide resin composition that the present invention relates to, the addition of plastifier if consider sufficient plasticity, when making the amount of (A) alkali solubility modified polyimide resin be 100 weight portions, is preferably 5 weight portions～30 weight portions.In addition, consider from the anti-flammability aspect of firming body, more preferably 5 weight portions～20 weight portions.In the photosensitive polymer combination that the present invention relates to, can contain the solvent of ability uniform dissolution and/or dispersion (A) alkali solubility modified polyimide resin, (B) emulsion, (C) fire retardant, (D) plastifier as required.As solvent, can use the solvent that uses in the above-mentioned modified polyimide resin composition.Photonasty modified polyimide resin composition of the present invention can be used for photosensitive film suitably.Consider that from the viewpoint of making photosensitive film the concentration of the modified polyimide in the photosensitive polymer combination is preferably 10 weight %～70 weight %.The concentration of modified polyimide is considered from the thickness aspect of photosensitive film, is preferably more than the 10 weight %, considers from viscosity, the film thickness uniformity aspect of photosensitive polymer combination, is preferably below the 70 weight %.Consider from the thickness aspect of resulting photosensitive film, more preferably 20 weight %～60 weight %.

Then the manufacturing approach to the photosensitive film that the present invention relates to describes.The photosensitive polymer combination that contains solvent that at first will the present invention relates to is coated on the base material.As above-mentioned base material, so long as the base material that when forming photosensitive dry film, can not damage does not then limit especially.As this base material, can enumerate silicon chip, glass, pottery, heat-resistant resin, carrier film etc.As the carrier film among the present invention, can enumerate polyethylene terephthalate film, metal film.Consider from the viewpoint that operability is good, be preferably heat-resistant resin and carrier film, press the fissility aspect after gluing to consider, be preferably the polyethylene terephthalate film especially from base material.Then, can obtain photosensitive resin film of the present invention through with the solvent seasoning in the resin combination that is coated with.Drying condition is not limited especially, can carry out about 10 minutes～60 minutes under the temperature about 60 ℃～130 ℃ usually.

Can use photosensitive polymer combination of the present invention to make the polyimide resin film of patterning.This method has and is coated on the base material and the step of film forming; The step that above-mentioned solvent is removed in resulting film heating; Above-mentioned composition to having removed solvent carries out step of exposing through mask; Be heated to the above step of solidification temperature of above-mentioned hardening agent after exposure back step of developing and the development.

Wherein, the method that photonasty modified polyimide resin composition is coated on the base material is not limited especially, for example can carry out, in addition, can enumerate spin coating, spraying, mouthful pattern coating, scraper coating, aniline printing etc. through serigraphy.Exposure can be carried out as follows, and through having the photomask of arbitrary graphic pattern, common radiant quantity radiation ultraviolet ray with 200～2000mJ, X ray, electron ray etc. carry out above-mentioned exposure thus.As developer solution, can use alkaline developer, for example the WS of inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammoniacal liquor etc.Develop and under about 15 ℃～60 ℃, carry out about 0.5 minute～10 minutes usually.The heating of carrying out for curing is carried out about 30 minutes～120 minutes under about 120 ℃～200 ℃ usually.In this method,, use printed wiring board, the FPC substrate carried out wiring, can form the printed wiring board with arbitrary graphic pattern or the diaphragm or the interlayer dielectric of FPC substrate thus as base material.Below they are further specified.

That is, in the preferred mode, the photonasty modified polyimide resin composition of the invention described above can be used to form the diaphragm of FPC, can be used to form photosensitive resin film simultaneously.This photosensitive resin film can come film forming through photosensitive polymer combination being coated on the first-class method of PET film of for example having implemented suitable demoulding processing.As coating process, can enumerate that rod is coated with, roller coat, mouthful pattern coating, scraper plate coating, dipping, scraper coating, spraying, showering, spin coating, seam are coated with, brushing etc.After the coating, the heat treated that is called preliminary drying through heating plate etc. is as required removed the solvent in the composition, can make photosensitive resin film thus.This photosensitive resin film can be used as the photosensitive dry film resist.So; During photosensitive film that use is made up of photosensitive polymer combination of the present invention; Carry out drying after being coated on arbitrarily on the base material with any means the solution of photosensitive polymer combination, form dry film, for example form laminated film with carrier film and photosensitive film.In addition, the coverlay cambium layer press mold of the antifouling arbitrarily usefulness of one deck, protection usefulness at least can be set on photosensitive film.In the laminated film that the present invention relates to, as coverlay, so long as the film of protection such as low density polyethylene photosensitive film does not then limit especially.

The positive light sensitivity modified polyimide resin composition of use the invention described above is made the method for the diaphragm (coverlay) of FPC and is carried out as follows; Being formed with on the FPC substrate of wiring this positive light sensitivity modified polyimide resin composition of coating after the film forming; Above-mentioned solvent is removed in resulting film heating, made public through mask then, further develop; Obtain heating behind the eurymeric pattern, the heat-resistant resin that dissolves in solvent is crosslinked.

The present invention also provides printed wiring board or the FPC with patterning polyimide resin film of making as stated in addition.

Below specify through embodiment and comparative example preparation method and characteristic thereof the polyimide solution that uses among the present invention.Polycarbonate modified polyimide, polyester modification polyimide, polyurethane-modified polyimide can not change aspect diol compound synthesis modification polyimide, therefore only the example that uses PCDL are described at this.In addition, owing to the polyimide that obtains having various characteristics through the combination of diol compound, diisocyanate cpd, tetracarboxylic dianhydride, diamines, so the present invention is not limited only to these embodiment.

Embodiment

Synthetic embodiment 1

On 2 liters separated type three-neck flask of the anchor type stirrer that stainless steel is installed, install and have the spherical cooling tube that moisture separates water trap.Add the デュラノー Le T5651 (PCDL that the ケミカ Le ズ of Asahi Chemical Industry (strain) produces) [molecular weight 986 (calculating)] of 98.60g (100 mM), the デュラネート D201 (diisocyanate that the ケミカ Le ズ of Asahi Chemical Industry (strain) produces) [molecular weight 532 (the weight % by isocyanates calculates)] of 106.40g (200 mM), the gamma-butyrolacton (γ BL) of 156g by hydroxyl value.After stirring 15 minutes under room temperature, nitrogen atmosphere, the 200rpm, be warming up to 140 ℃ and stirred 1 hour.Then add two (3,4-dicarboxyl phenyl) ether dianhydrides (ODPA) of 62.04g (200 mM), the γ BL of 156g, reacted 1.5 hours when stirring down at 170 ℃, 200rpm.Further; Be cooled to room temperature; 3 of ethylenebis (trimellitic acid) dianhydride of adding 28.73g (70 mM), 16.82g (60 mM); 3 '-diamido-4,4 of 4 '-dihydroxy-diphenyl sulfone (ABPS), 17.18g (60 mM), 4 '-diaminodiphenyl-methane-3; Two [4-(4-amino-benzene oxygen) phenyl] sulfones (BAPS) of 3 '-dioctyl phthalate (MBAA), 21.62g (50 mM), the ethyl benzoate of 312g, the toluene of 70g, the gamma-valerolactone of 3.0g (30 mM), the pyridine of 4.8g (60 mM) reacted 3.5 hours when stirring down at 170 ℃, 200rpm.Reflux except that going to system, is obtained the polyimide solution of 35% concentration thus.

Synthetic embodiment 2

Use the device identical, the デュラノー Le T5651 of adding 118.32g (120 mM), the hexamethylene diisocyanate (HDI) of 40.37g (240 mM), the gamma-butyrolacton (γ BL) of 165g with synthetic embodiment 1.After stirring 15 minutes under room temperature, nitrogen atmosphere, the 200rpm, be warming up to 140 ℃ and stirred 1 hour.Then add the ODPA of 55.84g (180 mM), the γ BL of 166g, reaction is 1.5 hours when under 170 ℃, 200rpm, stirring.Further; Be cooled to room temperature; Add 3,3 ', 4 of 35.31g (120 mM); The pyridine of the toluene of the MBAA of the ABPS of 4 '-biphenyl tetracarboxylic dianhydride (BPDA), 33.64g (120 mM), 17.18g (60 mM), the γ BL of 331g, 70g, the gamma-valerolactone of 3.0g (30 mM), 4.8g (60 mM), reaction is 4.5 hours when under 170 ℃, 200rpm, stirring.Reflux except that going to system, is obtained the polyimide solution of 30% concentration thus.

Synthetic embodiment 3

Use the device identical, 1 of the デュラノー Le T5652 [molecular weight 1972 (calculating)] of adding 157.76g (80 mM), 33.63g (160 mM), the γ BL of 5-naphthalene diisocyanate (NDI), 172g by hydroxyl value with synthetic embodiment 1.After stirring 15 minutes under room temperature, nitrogen atmosphere, the 200rpm, be warming up to 140 ℃ and stirred 1 hour.Then add the ODPA of 49.64g (160 mM), the γ BL of 171g, reaction is 1.5 hours when under 170 ℃, 200rpm, stirring.Further; Be cooled to room temperature; Add ethylenebis (trimellitate) dianhydride, the 40.36g (144 mM) of 32.83g (80 mM) ABPS, 6.57g (16 mM) 2; Two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, the triglyme of 228g, the toluene of 80g, the gamma-valerolactone of 2.5g (25 mM), the pyridine of 3.9g (50 mM) reacted 4.5 hours when stirring down at 170 ℃, 200rpm.Reflux except that going to system, is obtained the polyimide solution of 35% concentration thus.

Synthetic comparative example 1

Use the device identical, the デュラノー Le T5651 of adding 133.11g (135 mM), the HDI of 145.41g (270 mM), the γ BL of 155g with synthetic embodiment 1.After stirring 15 minutes under room temperature, nitrogen atmosphere, the 200rpm, be warming up to 140 ℃ and stirred 1 hour.Then add the ODPA of 55.84g (180 mM), the γ BL of 155g, reaction is 1.5 hours when under 170 ℃, 200rpm, stirring.Further; Be cooled to room temperature; Add the BPDA of 39.72g (135 mM), two [4-(4-amino-benzene oxygen) phenyl] sulfones (BAPS) of 77.85g (180 mM), the γ BL of 310g, the toluene of 70g, the gamma-valerolactone of 3.2g (32 mM), the pyridine of 5.0g (64 mM), reacted 3 hours when stirring down at 170 ℃, 200rpm.Reflux except that going to system, is obtained the polyimide solution of 35% concentration thus.

The rerum natura of the polyimide resin that obtains in above-mentioned synthetic embodiment, the synthetic comparative example is measured through following method, and the result is shown in below table 1.

Number-average molecular weight Mn with modified polyimide resin of copolymerization polycarbonate structure produces through gel permeation chromatography GPC 1-amino-2-naphthol-4-sulfonic acid Dong ソー society, HLC-8220GPC) measures weight-average molecular weight (Mw), number-average molecular weight (Mn), disperses (Mw/Mn).The TSKgel GMHHR-H that pillar uses Dong ソー society to produce, as carrier solvent, use concentration with 0.1N in NMP is dissolved the solvent that LiBr forms.The scaled value that molecular weight is to use polystyrene standard (TSK polystyrene standard) to calculate.

The sample that is used to measure glass transition temperature Tg, heat decomposition temperature, length growth rate, elastic modulus is made as follows: the Copper Foil F2-WS (18 μ m) that produces in Furukawa サーキット Off ォイ Le Co., Ltd.; Be coated with the film that forms thickness 15 ± 2 μ m through serigraphy; With this film 120 ℃ of following dryings and thermal treatment 60 minutes; Then, the Copper Foil etching is removed, thus the perparation of specimen 180 ℃ of following dryings and thermal treatment 30 minutes.

The sample that is used to measure warpage properties is made as follows: be coated with through serigraphy on the カプト of 25 μ m thickness Application film that to form thickness be the film of 15 ± 2 μ m; This film is following dry 60 minutes at 120 ℃; Then descended dry 30 minutes, thus the perparation of specimen at 180 ℃.The come-up of the end through sample is highly estimated, and highly for to count ◎ below the 1mm, highly for to count zero below the 10mm, highly above for 10mm and situation that can measure is designated as △, warpage to the situation of not measurable degree be designated as *.

The sample that is used to estimate chemical proofing is to use except not with likewise making the sample that obtains with the glass transition temperature Tg test sample the Copper Foil etching.The chemicals of being investigated is sodium hydrate aqueous solution and the organic solvent MEK of 1N.The situation that film surface is glossy and do not have a minimizing of thickness is designated as ◎, and the situation about being reduced to below the 0.1 μ m of thickness is designated as zero, and the situation that is reduced to 0.2～0.9 μ m of thickness is designated as △, and the above situation of 1.0 μ m that is reduced to of tarnish or thickness is designated as *.

[table 1]

The rerum natura of the polyimide resin of synthetic embodiment and synthetic comparative example

?	Unit	Embodiment 1	Embodiment 2	Embodiment 3	Comparative example 1
						Diisocyanate	?	D201	HDI	NDI	HDI
Soft construction weight ratio	%	61	56	52	54
						Number-average molecular weight Mn	?	11000	9000	42000	21000
Glass transition temperature Tg	℃	87	97	140	122
						Heat decomposition temperature (reducing by 5% weight)	℃	287	315	328	289
Length growth rate	%	>;200	>;200	>;200	>;200
						Elastic modulus	GPa	1.06	1.15	0.69	0.61
Warpage properties	?	○	○	○	◎
						Chemical proofing	?	○	△	◎	○

Embodiment 1～8, comparative example 1～3

The preparation of positive type photosensitive organic compound

In each varnish (basic varnish) that in synthetic example 1～2 and synthetic comparative example 1, obtains, with respect to the cooperation as shown in table 2 of polymer solids composition as the naphthalene quinone di-azide sulfonic acid ester of emulsion (ダイトーケミッ Network ス society produces: DTEP-350, PA-6, the synthetic society of Japan produce: 4NT-300), as fire retardant EXOLIT OP 935) and mix and prepare photonasty modified polyimide resin composition (photosensitive ink) (big

chemical society produces: SPB-100, big eight chemical industry societies produce: PX-200, Network ラリア Application De ジャパ Application society produce:.And, add levelling agent (the サイテッ Network society production: XL480), after finally mixing, carry out deaeration under the vacuum, obtain positive light sensitivity modified polyimide resin composition of about 1wt% with respect to the polymer solids composition.

The evaluation of development property: sensitization is developed and is tested

Be coated on each the positive light sensitivity modified polyimide resin composition that so obtains on the Copper Foil F2-WS (18 μ m) of Furukawa サーキット Off ォイ Le Co., Ltd. production through silk screen print method; Preliminary drying (90 ℃ * 30 minutes) is removed the solvent in the composition then, obtains the photoresist epithelium of thickness 13～17 μ m.The test pattern that placement eurymeric photomask is used on the coated film of this cooperation photoresist (10,15,20,25 ..., 200 microns through hole and line & spacing (line & space) pattern); Use 2kW ultrahigh pressure mercury lamp irradiation unit オー Network to make institute's goods: JP-2000G), to shine with the exposure that can obtain image.The sample that will shine with 500～2000mJ is with developer solution (2% sodium hydrate aqueous solution) spray development.Under the irradiation of 1000mJ, carry out developing in 0.5～3 minute, use deionized water wash, after the hot-air drying stove drying, observe resolution with 40 ℃ developer solutions.This polyimide coating film is about 16 microns at 30 minutes polyimide thickness of 60 minutes, 180 ℃ following dried of 120 ℃ of following dried.The bore of the through-hole pattern of the multipolymer polyimide coating film that obtains through said method and the live width result of line & spacing (line & space) pattern are as shown in table 2.

[table 2]

Notes 1) use level of emulsion, fire retardant and foam-breaking agent is the addition (weight portion) with respect to polyimide resin solid constituent 100 weight portions.

Embodiment 1～6 and comparative example 1～4

For the photonasty modified polyimide resin composition shown in the above-mentioned table 2, to following project implementation evaluation, its result is shown in below table 3.

Subduing property

The stainless steel version of each anti-flammability modified polyimide composition with 165-3D order (mesh) is coated on the substrate through serigraphy; Carry out preliminary drying (90 ℃ * 30 minutes) through hot-air oven and remove the solvent in the composition, obtain the photoresist epithelium of thickness 14～17 μ m.This is combined with filming of photoresist carries out developing in 2 minutes with 40 ℃ developer solution, use deionized water wash, 120 ℃ of following dried 60 minutes, 180 ℃ of following dried 30 minutes, resulting polyimide film thickness was about 15 μ m with hot-air oven.For resulting polyimide film, with 180 ° of coated face bendings laterally, range estimation judges that desciccator diaphragm has flawless.Determinating reference is as follows.

Zero: the desciccator diaphragm flawless.

◎: desciccator diaphragm cracks or chaps.

The soldering thermotolerance

Test method(s) according to JISC-6481; It is last through above-mentioned film manufacturing method each photonasty modified polyimide composition of the embodiment shown in the table 2 1～6 and comparative example 1～4 record to be coated on substrate [(registered trademark) ESPANEX, Nippon Steel's chemistry (strain) system] MC18-25-00FRM, makes test and uses sample.With coating rosin based scaling powder (flux) on resulting test film; In 260 ℃ braze are bathed floating 5 seconds as 1 circulation; Each circulation visual observations desciccator diaphragm; Confirm not have " expansions ", " peeling off " and " braze pierces ", the maximum cycle when fully finding variation during with repetition is represented.

Flammability

The burning test sheet is through following method manufacturing.The desciccator diaphragm of the photonasty modified polyimide composition of embodiment 1～6 shown in the above-mentioned table 2 of thickness 20 μ m and comparative example 1～4 record is set on the two sides of the polyimide film of thickness 25 μ m, 200mm * 50mm (eastern レデュ Port Application (strain) is produced, カプト Application 100EN), with it as test film.Combustion characteristics is to estimate anti-flammability through the method according to the flame retardant test standard 94UL-VTM test of the macromolecular material of U.S. Underwriters Laboratories Inc. (abbreviating UL as).

" VTM " in the table 3 and " NOT " are based on following benchmark.

VTM-0: satisfy all following items that require.

(1) the Total Test sheet connects in each time and can not produce flaming combustion above 10 seconds after flame is ended.

(2) 5 test films of each group are amounted to 10 times the flame that connects, the total of flaming combustion time is no more than 50 seconds.

(3) there is the burning of flame or red heat can not reach the graticule of 125mm.

(4) absorbent cotton can be owing to there being the flame dropping to catch fire.

(5) connect for the second time flame and end after, the total that flame and red heat are burnt that has of each sample is no more than 30 seconds.

In (6) 1 groups of 5 test films only during 1 undesirable item or have the flame time add up to 51 seconds～55 seconds the time, further 5 test films are made an experiment, all test films satisfy above-mentioned (1)～(5).

VTM-1: satisfy all following items that requires.

(1) the Total Test sheet connects in each time and can not produce flaming combustion above 30 seconds after flame is ended.

(2) 5 test films of each group are amounted to 10 times the flame that connects, the total of flaming combustion time is no more than 250 seconds.

(5) connect for the second time flame and end after, the total that flame and red heat are burnt that has of each sample is no more than 60 seconds.

In (6) 1 groups of 5 test films only during 1 undesirable item or have the flame time add up to 251 seconds～255 seconds the time, further 5 test films are made an experiment, all test films satisfy above-mentioned (1)～(5).

VTM-2: satisfy all following items that requires.

(4) absorbent cotton might catch fire because the flame dropping is arranged.

NOT: above grade is all defective.

HHBT patience

Upward through serigraphy each anti-flammability modified polyimide composition is coated on the substrate at the IPC-C of commercially available substrate (IPC specification) (comb type pattern) with 165-3D purpose stainless steel version; Heated 60 minutes down at 120 ℃ with hot-air oven, heated 30 minutes down at 180 ℃.This test film is applied DC current 100V under 85 ℃, the atmosphere of relative humidity 85%.The interior insulating resistance value of measuring after 1000 hours of layer estimated HHBT patience.The mensuration of insulating resistance value is after applying the 100V DC voltage and keeping 1 minute, applies at this voltage and utilizes the electrical isolation meter to carry out under the state.Determinating reference is as follows.

Zero: insulation resistance is the above situation of 108 Ω.

*: insulation resistance is less than the situation of 108 Ω.

[table 3]

?

Embodiment 1

Embodiment 2

Embodiment 3

Embodiment 4

Embodiment 5

Embodiment 6

Embodiment 7

Embodiment 8

Comparative example 1

Comparative example 2

Subduing property (180 ° of bendings)

＞20 times

Soldering thermotolerance (260 ℃ * 5 seconds)

5 times

Flammability (UL94VTM)

VTM-0

HHBT patience

○

The evaluation of printing

Printing uses the test of ピーアイ with full version mask ( ), and the MT-550TVC screen process press that uses マイ Network ロテッ Network society to produce carries out.In addition; For estimating employed galley; Use the test of ピーアイ technical institute with the frame size of printing screen (the stainless steel of 165 orders-3D, the thick 10 μ m of emulsion) (550mm * 650mm) edition; At setting printing condition is that sdueegee speed 50～100mm/min, version spacing (clearance) are to print under 0.1～0.2MPa for 1.5mm～2.0mm, sdueegee coining, carries out evaluating characteristics for following project.

After carrying out 20 one way printings (shot) continuously on the copper base, at room temperature carry out 5～10 minutes levelling, with 90 ℃ of hot-air oven heating 30 minutes, estimate through range estimation and optical microscope.Estimate " profit of spreading and sinking in (ニジミ) ", " style of calligraphy characterized by hollow strokes (か The れ) ", " blank (ボイ De) or damaged (カケ) " and " rollability ローリ Application グ property) (when sdueegee moves thickener on silk screen in the front of the direct of travel side of sdueegee, the rotation status so that roughly cylinder state rotating flow moves bad) " carry out.The result is as shown in table 4.

[table 4]

Continuous printing

During this is estimated, whether can print continuously and estimate for 100 times not changing thickness.Print an above-mentioned full version pattern continuously; Begin to the 10th one way printing from printing; Thereafter the pattern sample is extracted in per 10 one way printings out till the printing of 100 one way, with above-mentioned same condition under carry out drying after, likewise estimate and use the observation by light microscope shape with above-mentioned.Their result is as shown in table 5.And zero seal of the continuous one way printing in the table is meant good film shape, and * seal is meant bad film shape.Wherein, end printing during the remarkable variation of film shape.

[table 5]

Result by table 4 and table 5 can know that printing of the present invention is excellent with continuous printing with the film shape of photosensitive polyimide printing ink.

FPC makes

With the positive light sensitivity modified resin composition serigraphy of embodiment 1～8 and comparative example 1～3 on the FPC substrate as the photonasty protective seam after; Carry out preliminary drying; Make public, develop, afterwards dry by the fire the step of (120 ℃ * 60 minutes+180 ℃ * 30 minutes) then successively, further implement the FPC that the electrolytic gold plating manufacturing has diaphragm then.

Gold-plated processing

Carry out through common electrolytic gold plating and the processing of electroless plating gold.That is, carry out according to the sequence of steps shown in following.Specifically, sample is immersed in successively in the groove of each step after, carry out drying.

The electrolytic gold plating treatment step

Ungrease treatment (acid or alkaline degreasing), washing, acid treatment, washing, soft etching, washing, pre-preg (acid treatment), washing, electrolytic ni plating (watt is bathed), washing, electrolytic gold plating (potassium auricyanide), washing, drying

Electroless plating gold treatment step

Ungrease treatment (acid or alkaline degreasing), washing, acid treatment, washing, soft etching, washing, pre-preg (acid treatment), palladium chloride catalystization, washing, electroless plating nickel treatment step (nickel nitrate), washing, electroless plating gold (potassium auricyanide), washing, drying

The evaluation of layered product

Base material as flexible printing wiring board; Use エスパネッ Network ス M (Nippon Steel's chemistry (strain) is produced) (thickness of insulating layer 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)), make line/spacing: the comb type wiring plate of 30/30 μ m, 50/50 μ m, 100/100 μ m, 200/200 μ m.Printing positive light sensitivity modified polyimide composition carries out preliminary drying on this circuit board.Plating partly uses mask to make public, develop, afterwards dry by the fire the step of (120 ℃ * 60 minutes+180 ℃ * 30 minutes).In exposure, development step, carry out electrolytic ni plating-Jin or electroless plating nickel-Jin at opening portion, about 3～5 μ m of the thickness of nickel, about 0.03～0.07 μ m of thickness of gold.Coating is confirmed through little x-ray fluorescence analysis or cross-section to the infiltration of inside by peristome.Its result is as shown in table 6.

[table 6]

The plating test findings

Industrial applicibility

Positive light sensitivity modified polyimide composition of the present invention is suitable as the photosensitive ink that is used on electronic component, forming film; This film is to be used for forming as the flexible distributing board that uses in the guidance panel of various electronic devices etc. or the protective seam of circuit substrate at electronic applications; The insulation course of laminated substrate forms, and the parts of the silicon chip that uses in the semiconductor device, semi-conductor chip, semiconductor device periphery, semiconductor-chip-mounting are with substrate, heat liberation board, pin pin! リー De ピ Application), the protection or the insulation and bonding of semiconductor self etc.

Lining for as the electronic material parts such as coating material of internal layer lining material, liquid crystal orientation film, IC or the LSI of the surface-coated material of in the past flexible printed board, multilayer rigid substrates is used polyimide film with the surface protection film or the interlayer dielectric of industrial materials, in the past for methods such as laser-induced thermal etching or plasma etching are carried out in the assigned position perforate of diaphragm.Yet though positional precision is very good, perforate needs the time, has device, shortcoming that operating cost is high.In recent years, use the technology fast development of the light seal method of photosensitive polyimide, therefore image is formed step further simplifies widespread use polyimide in electronic applications.If use photosensitive polyimide ink composite of the present invention, then through make public, step of developing, can realize that fine pattern processing forms than in the past the simpler image of photo-engraving process.

Claims

1. photonasty modified polyimide resin composition contains modified polyimide, emulsion and the thermal curing agents shown in the formula (I),

[Chemical formula 1]

Figure 2010800295544100001DEST_PATH_IMAGE001

In the formula; R representes independently that respectively carbon number is 1～18 alkylidene, and X representes carbonate group, ester group or urethane groups respectively independently, and Y representes independently that respectively carbon number is 1～18 alkylidene or arlydene; A representes to remove the divalent organic group that the amino of diamines forms; The quadrivalent organic radical group that the carboxyl of tetrabasic carboxylic acid forms is removed in Z and Z ' expression, and among A, Z and the Z ' any at least one has free hydroxyl and/or carboxyl, and m, p, q represent 1～20 integer independently of each other.

2. composition according to claim 1, wherein, said emulsion is the positive type light sensitive agent.

3. according to claim 1 or claim 2 composition wherein, further has reactive group in the end portion of the modified polyimide shown in the said general formula (I), and this modified polyimide has Thermocurable thus.

4. like any described composition in the claim 1～3; Wherein, The ratio of the repetitive that the number of repeat unit in the said general formula (I) is represented with said n and the weight of the modified polyimide shown in the said general formula (I) (when wherein, Y is aromatic series except the weight of Y) is 0.3～0.7.

5. like any described photonasty modified polyimide resin composition in the claim 1～4, wherein, said emulsion is the naphthoquinones two nitrine sulfonyl esters or the two nitrine naphtoquinone compounds of aromatic polyhydroxy compounds.

6. like any described composition in the claim 1～5, wherein,, further contain non-halogenated flame retardant 1～20 weight portion with respect to said modified polyimide 100 weight portions.

7. like the said composition of claim 6, wherein, said non-halogenated flame retardant is hydrated metal compound, phosphate based compound or the phosphonitrile based compound of the metal hydroxides of non-halogen system etc.

8. photosensitive resin film through with any described composition film forming in the claim 1～7, is removed resulting film heating said solvent and is obtained.

9. the manufacturing approach of patterning polyimide resin film; Has the step that any described composition in the claim 1～7 is coated on film forming on the substrate; The step that said solvent is removed in resulting film heating; Said composition to having removed solvent carries out step of exposing through mask, is heated to the above step of solidification temperature of said hardening agent after exposure back step of developing and the development.

10. method as claimed in claim 9, wherein, said base material is printed wiring board or the FPC substrate that is formed with wiring.

11. printed wiring board or FPC have the patterning polyimide resin film of making through the described method of claim 10.